A Density Functional Study of the Hydrophobicity of Silicalite By Diana Wamakima A Major Qualifying Project Report Submitted to the faculty of the WORCESTER POLYTECHNIC INSTITUTE In partial fulfillment of the requirements for the Degree of Bachelor of Science In Chemical Engineering 28 April, 2010 APPROVED ________________________ Prof. Nathaniel A. Deskins Abstract Factors that influence water adsorption in silicalite were studied. It was found that the energy of adsorption becomes less stable as water molecules are loaded in the silicalite structure. A structure with one water molecule was found to have an energy of -14.42KJ/mol while one with three molecules was - 8.6 KJ/mol. It was also demonstrated that water prefers to diffuse through the larger 10 ring channels as opposed to the small 4 ring channels. 2 Table of Contents 1) Abstract .................................................................................................................................................. 2 2) Table of Figures ...................................................................................................................................... 4 3) Table of Tables ........................................................................................................................................ 4 4) Introduction ............................................................................................................................................ 5 5) Background ............................................................................................................................................. 7 a) Zeolites ............................................................................................................................................. 7 b) Silicalite .......................................................................................................................................... 11 c) Water in Silicalite ........................................................................................................................... 14 d) Quantum Mechanics ...................................................................................................................... 16 e) Density Functional Theory ............................................................................................................. 17 6) Methodology ........................................................................................................................................ 20 a) System Set-up ................................................................................................................................ 20 b) CP2K ............................................................................................................................................... 20 i) Potentials ................................................................................................................................. 22 ii) Basis Sets ................................................................................................................................. 22 iii) Wave function Optimization ................................................................................................... 22 7) RESULTS AND DISCUSSION ................................................................................................................... 24 a) Lattice Energy Minimization .......................................................................................................... 24 b) Effect of Loading on the Energy of Adsorption .............................................................................. 25 c) Effect of Position of Water Molecule on the Energy of Adsorption .............................................. 27 8) Conclusions and Recommendations .................................................................................................... 31 9) Bibliography .......................................................................................................................................... 33 10) Appendices ........................................................................................................................................... 35 a) Appendix A: Sample Energy of Adsorption Calculations ............................................................... 35 b) Appendix B: Sample CP2K Input File .............................................................................................. 36 c) Appendix C: Force field Parameters for Lattice Energy Minimization ........................................... 44 3 Table of Figures Figure 1: Example of Zeolite (Zeolite A) (Dyer) ............................................................................................. 7 Figure 2: Aluminosilicate Tetahedra (Dyer) .................................................................................................. 9 Figure 3: Secondary Building Units (Baerlocher and B.) ............................................................................. 10 Figure 4: Silicalite Crystalline Structure ...................................................................................................... 11 Figure 5: MFI Structure (Baerlocher and B.) ............................................................................................... 11 Figure 6: Channels in Silicalite (Ramachandran, Chempath and J.) ............................................................ 12 Figure 7: Channels in Silicalite ..................................................................................................................... 13 Figure 8: The lattice energy is plotted as a function of unit cell volume. Results were calculated using DL_POLY ...................................................................................................................................................... 24 Figure 9: Effect of Water molecule loadings on the Energy of Adsorption ................................................ 26 Figure 10: Water molecule located in a pore with a diameter of 1.004nm where E is the energy if adsorption and d the diameter of channel ................................................................................................. 27 Figure 12: Water molecule located in a pore with a diameter of 0.802nm ............................................... 28 Figure 13: Water molecule located in a pore with a diameter of 0.574nm ............................................... 28 Figure 14: Water molecule located in a pore with a diameter of 0.438nm ............................................... 29 Figure 15: Water molecule located in a pore with a diameter of 0.454nm ............................................... 29 Table of Tables Table 1: Unit Cell Dimensions ..................................................................................................................... 25 Table 2: Summary of Energy of Adsorption Values .................................................................................... 35 Table 3: Buckingham Potentials .................................................................................................................. 44 Table 4: Screened Harmonic Potentials ...................................................................................................... 44 4 Introduction Silicalite is one of the most studied zeolites that has both hydrophobic and organophilic selectivity (Ramachandran, Chempath and J.). Hydrophobic in this case does not mean water repelling but that the water-water interaction (Labar, Fuchs and Adamo) is much larger than the water-zeolite interaction. It has been widely used to clean up water contaminated with organic compounds. Understanding the behavior of water in hydrophobic micropores is important in a wide variety of fields, ranging from biological membrane transport to applications in carbon nanotubes. Silicalite is a pure silica MFI structure (Ramachandran, Chempath and J.). Ideally, silicalite would be electrically neutral if it was only composed of silicon and oxygen atoms. It is widely regarded as a hydrophobic structure. Earlier studies showed that silicalite readily adsorbs organic molecules over water. These studies as well as later studies have shown that silicalite actually adsorbs a small amount of water. This should not be the case if silicalite is electrically neutral Studies have demonstrated that silicalite, also contains aluminum which causes a charge imbalance and therefore favoring water adsorption. The degree of aluminum substitution and its corresponding effect on water loading in the silicalite structure has been an area of interest (Yazaydin). Molecular simulations performed have shown that a perfect silicalite structure is hydrophobic and does not adsorb water at low pressures (Ramachandran, Chempath and J.). When pressure is increased, the pores become saturated with water molecules at some intermediate pressure. The presence of hydrophilic defects, like the aluminum substitution mentioned previously lead to adsorption of small amounts of water at low pressures. Previous studies have demonstrated that the silicalite structure can adsorb up to 8-9 water molecules in its structure (Fleys). The objective of this research project is to investigate the factors that affect the hydrophobicity of silicalite using density functional theory (DFT). To the best of my knowledge most molecular simulation 5 studies have been performed using molecular dynamics and Monte Carlo methods. DFT uses a different approach from